Monoazo dye containing a trifluoro acetylamino group



Patented Feb. 17, 1948 MONOAZO DYE CONTAINING A TRIFLUORO ACETYLAMINO GROUP Joseph B. Dickey, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application March 2, 1944, Serial No. 524,773

7 Claims.

This invention relates to azo dyes and to a 7 process for the preparation thereof.

Azo dyes of the following general formula have seen prepared:

I. X R

R3 HN-C O-CHa wherein R represents an aryl group of the benzene series, R1 represents an alkyl group, R2 represents hydrogen, an alkyl group or a hydroxyalkyl group, R3 represents an alkyl group or a hydroxyalkyl group and X represents oxygen or sulfur.

I have now succeeded in preparing azo dyes resembling the aforesaid dyes, but differing in that the acetamino group is replaced by a trifluoroacetylamino group. My new dyes have greatly increased light-fastness on cellulose acewherein R represents an aryl group of the benzene series, R1 represents an aliphatic alcohol radical, R2 represents hydrogen or an' aliphatic alcohol radical, R3 represents an aliphatic alcohol radical and X represents oxygen or sulfur, by condensing a diazonium salt of a primary amine of the benzene series with a coupling com ponent of the following general formula:

wherein 2!, R1, R2 and R: have the values set forth abovein connection with Formula II.

2 The azo dye compounds having the following general formula:

z xn,

I I /Ra Ra Z1 HNO O- C F:

wherein Z represents a member selected from the group consisting of hydrogen and 5 nitro group, Z represents a member selected from the group consisting of halogen, a cyano group, a hydroxyl group, an aliphatic acyl group, an alkylsulfonyl group, a sulfamyl group, a sulfamyl group in which one hydrogen has been replaced by an aliphatic alcohol radical, a sulfamyl group in which each hydrogen has been replaced with an aliphatic alcohol radical, and a trifluoromethyl group, R1 represents an alkyl group, and R2 and Rs each represents an aliphatic alcohol radical, appear to be particularly advantageous.

Typical of the primary amines which are diazotized and coupled with the compounds of Formula III are: o-nitroaniline, o-fluoro-pnitroaniline, o-chloro-p-nitroanilin-e, o-bromo-pnitroaniline, o-cyanopnitroaniline, 2-amino-5- ,nitrophenyl-methyl' ketone, 2-amino-5-nitrm phenylmethyl sulfone, 2-amino-5-nitrobenzene- N-ethylsulfo'namide, o-trifluoromethyl-p.-nitroaniline, 2,4-dinitroaniline, 2,4-dinitro 6 fluoroaniline, 2,4-dinitro-6-chloroaniline, 2,4-dinitro- 6-bromoaniline, ZA-dinitro-fi-iodoaniline, 2,4-

dinitro-6-hydroxyaniline, 2,4-dinitro G-cyanoaniline, 2amino-3,5-dinitrophenylmethyl ketone, 2-amino-3,5-dinitrophenylmethyl sulfone, 2 amino-3,5 dinitrobenzene-N-methylsulfonamide, 2 amino-3,5 dinitrobenzene-N-ethylsulfonamide and 2-amino-3,5-dinitrobenzene-N-(cmethoxyethyl) -sulfonamide. Typical of the coupling components represented by Formula IIi (above) which are employed in practicing my invention are: 2-methoxy 5 trifluoroacetylamino-N-ethylanlline, 2- ethoxy-5 -trifluoroacetylamino-N- (p-hydroxyethyl) aniline, z-(c-methoxyethoxy)-5-trifiuoroacetylamino N-(p-hydroxyethyl) -aniline, 2-(19- hydroxyethoxy) 5 trifiuoroacetylamino-N-(B- hydroxyethyl) -aniline, 2 methylmercapto-S-trifluoroacetylamino-N- (p-hydroxethyl) -a'niline, 2- methoxy-5 trifluoroacetylamino N-(Y,fi-dihydroxypropyl) -aniline, 2-ethoxy-5-trifiuoroacetylline, 2-trifluoromethylthio-B-trifluoroacetylam-.

ino -N- pmdihydroxypropyl) -aniline or Z-methylthiotrifluoroacetylamino N,N di (B-hydroxyethyl) -aniline. The following examples will serve to illustrate my new dyes and the manner of obtaining the same.

Example 1.--4-(o-fluoro p nitrophenylaeo) -2- L methory 5 trz'fluoroacetyZaminoN,N-cli-(5-.

hydroxy-ethyl) -am'line CHaCHsOH CHzCHzOH F HN-OO-GFa 15.6 g. (0.1 mole) of o-fiuoro-p-nitroaniline were suspended in 100 g. oi'water and 20 g. of concentrated hydrochloric acid. The mixture was cooled to 0-5 C. by adding ice. Diazotization was efiected by adding 6.9 g. of sodium nitrite-dissolved in 30 cc. of water. The cold diazo solution was added to an iced solution of 32.2 g. (0.1 mole) of 2methoxy-S-trifluoroacetylamino- N,N-di-(c-hydroxyethyl) -aniline in 150 cc. of acetic acid. The mineral acid was neutralized'by adding sodium bicarbonate. The resulting mixture was diluted with water to precipitate the dye. The dye was filtered ofi, washed and dried. It colored cellulose acetate rayon fabrics rubine shades from an aqueous suspension of the dye.

Example 3.- -4-(6 cyano-2,4-dinitrophenylazo) 2 trifluoromethylthio-5-trifluoroacetylamino- N ,N -dz'- p-hydromypropyl) -am'line on N02 sore A, I I 0Hi HCH:

i CHZCHCHZ ON HN-CO--CFs H 7.6g. ofsodium nitrite (dry) wereadded slowly with vigorous stirring to 50 cc. of sulfuric acid (95-96 per cent). The resulting mixture was stirred until a clear solution of nitrosyl sulfuric acid wasobtained; The solution cooled to 12 to 14 C.' and 120 g. of acetic acid were added with stirring. Then 20.8 g. (0.1 mole) of 6-cyano-2,4- dinitroaniline and 100 g. of acetic acid were added 'to'the"mixturesimultaneously with stirring, at

15 C. Stirring at 15" C. was continued for 2 hours. The resulting diazo solution was poured onto 250 g. of ice. The resulting iced solution was addedt'o a cold (10 C.) mixture of 37.2 g. (0.1

Example 2.4-(6-0hloro-2,4-dinitrophenylazo) Y 2 methomy-S-trifluoroacetyZamino-MN-di-(13- hydrocryethyl) -am'line 7 .6 g. of sodium nitrite (dry) were'added slowly with vigorous stirring to 50 cc. of sulfuric acid (95-96 per cent). -The-resulting mixture was stirred'until a-clear solution of nitrosyl sulfuric acid was obtained. Thesolution was cooled to 12 to 14 C. and 120 g. of acetic acid were added with stirring. Then 21.? g. (OI-mole) of 6- chloro ZA-dinitmaniline and 100 g. of acetic acid were added to the mixture simultaneously with stirring, at 15 C. Stirring at 15 C. was continued for 2 hours. The resulting diazo solution was poured onto 250 g. of ice. To the resulting iced solution'was added an iced solution of 32.2 g. (0.1 mole) of 2-methoxy-S-trifiixoroacetylamino- N,N-di-(e-hydroxyethyl)-aniline dissolved in 20 cc. of'concentrated hydrochloric acid and 70 cc. of water; The mineral acids were neutralized by immediately addin'gsodium acetate. The mixture was dilutedwith water tjojprecipitate the dye; The dye was then filtered off, washed with" water and dried. It colored cellulose acetate rayon fabrics greenish blue from an aqueous suspension of the dye.

mole) of 2-trifluoromethylthio-5-trifluoroacetyl amino-N,N-di-(e hydroxypropyl) aniline prepared by dissolvingthe aniline derivative in 200 g. of acetic acid and adding 92.2 g. of sodium carbonate. After coupling is complete (2 to 3 hours), the mixture was diluted with water to precipitate the dye. The dye was filtered ofi, washed with water-and dried. It colored cellulose acetate rayon fabrics greenish blue shades from an aqueous suspension of the dye.

Example 4.'-4 [2,4-dinitro-6-(N-ethylsulfamyl)- phenylaeol-2-methoxy-5-trifiuoroacetyZamino- N {LY-dihydrorzlfiropylaniline 265 cc. of sulfuric acid -96 per cent) were cooled in anice bath.- 41 g. of dry sodium nitrite were added to the cooled sulfuric acid with vigorous stirring over a' period of about 1 minute. The resulting mixture was stirred until a clear solution of nitrosylsulfuricacid was obtained. The mixture was cooled to 12 to 14 C. and 670 cc. of cooled acetic acid were added.- The resulting mixture was chilled to 1* C. and 50 g. of 2.4-dlnitro-fi-(N-ethylsulfamyl)-aniline were added. 106 g. of 2,4-dinitro-6-(N-ethylsulfamyl) -aniline were added together with-.530 cc. of acetic acid, keeping the temperature at 4 to 5 C. The resulting mixture was stirred at 4 to 5 C. for about 2 hours. The resulting solution was then poured into 10 liters of ice water. The resulting precipitate was filteredby suction and washed with water to'remov'e acid. The precipitate was then suspended in 1.2 liters of'acetic acid-and the suspension cooled to 0 C. To this suspensionwere added 156 g; of2-methoxy-5-trifl'uoroacetylamino-N-B,Y-dihydroxy' propylaniline dissolved in 200 cc. of cold acetic acid. 'The'resulting mixture washeld at 4 to 8" C. 'for 4' hours and was then allowed to stand at 20 to 25 C. for 12 hours. The dye was precipitated by Douring the mixture into 'cold water, with stirring. Sodium carbonate was added to the resulting aqueous mixture to neutralize the mineral acid. The dye was filtered olT by suctionv and dried at 20 to 25 C. The dye" coloredcellulose acetate rayon fabric blue from ana'queous suspension of aniline. (11) 2-methoxy-5-trifluoroacetylamino-N,N-di-(B-hydroxyethyl)- l in ethers, such as methyl cellulose, ethyl cellulose and benzyl cellulose,

The azo dyes of my invention are, for the most part, relatively insoluble in water and, accordticing my invention can be prepared by first condensing paminophenylethers or thioethers, e; g.,

p-methoxyaniline, p-ethoxyaniline or p -methylthioaniline, with trifiuoroacetyl chloride.

ingly, they may be advantageously directly applied to the textile material undergoing coloration in the form of an aqueous suspension which can be prepared by grinding the dye to a paste The resulting trifiuoroacetylamino derivative is 19 then nitratedwith nitric acid and sulfuric acid to give a mononitro derivative in which the nitro group is ortho to the ether group. The mononitro compound is then reduced by hydrogenation in methyl alcohol, in the presence of a nickel catalyst, at 50 to 100 C, p-Trifiuoromethylthioaniline can be prepared by nitrating trifiuoromethylbenzene with nitric acid and sulfuric acid and then reducing the p-trifiuoromethylnitro' benzene in methyl alcohol, with hydrogen and a nickel catalyst, at 50 to 100 C.

Diazo components, such as 2-amino-3,5-dinitrobenzene-N-methyl-, N-ethylor N-(p-methoxyethyl)-sulfonamide can be prepared by condensing 2-chloro-3,5-dinitro-1-sulfonyl chloride with a primary monoamine at a temperature below C. and then condensing the resulting sulfonamide with ammonia, as described in the copending application of James G. McNally and Joseph B. Dickey, Serial No. 401,972, filed July 11,

1941, now U. S. Patent 2,358,465, issued September 19, 1944.

The azo dyes of my invention are of greatest utility for the coloration of textile materials comprising organic derivatives of cellulose. However, they may be employed for the coloration of non-vegetable textile fibers, in general. Thus, they can be used to color organic derivatives of cellulose, silk, wool, nylon, vinyl acetate-vinyl chloride copolymers and protein synthetic wools.

be colored.

Typical organic derivatives of cellulose that can be colored include the hydrolyzed, as well as the unhydrolyzed, cellulose carboxylic esters, such as cellulose acetate, cellulose propionate and -Also cellulose ester and cellulose ether lacquers,' as well as lacquers from polyvinyl compounds can in the presence of a sulfonated oil, soap or other suitable dispersing agent, and dispersing the resulting paste in water. In some instances, the compounds may possess sufiicient solubility in water to render the use of a dispersing agent unbe conducted at temperatures of about 75 to 85 0., but any suitable temperature may be used.

Thus, the textile material to be dyed or colored is ordinarily added to the dyebath at a temperature lower than that at which the main portion of the dying is to be effected, a temperature of from to 55 C., for example, .fOllOWl'Ilg which the temperature is raised to that selected for carrying out the operation. The temperature at which the process is continued may vary somewhat depending upon the particular material undergoing coloration. As is understood by those skilled in the art, the intensity of dyeing can be varied by varying the proportion of dye to the material undergoing preparation, Generally speaking, I to 3 per cent by weight of dye to material is employed, although any desired proportions can be used.

Suitable dispersing agents are disclosed in U. S. Patent 2,115,030, issued April 26, 1938. The process disclosed in the aforesaid patent for the dyeing of cellulose acetate can be used in applying the dyes of the present invention to cellulose acetate. While a satisfactory method for dyeing has been disclosed herein, it will be understood that any other suitable methods for dyeing the non-vegetable textile materials named herein cellulose butyrate, and the hydrolyzed, as well as the unhydrolyzed, mixed cellulose carboxylic esters, such as cellulose acetate propionate and can be employed. Lacquers may be colored with the dye compounds of my invention by the methods customarily employed in the lacquer art. a V

The colors which can be obtained on textile materials comprising cellulose acetate with representative of my new dyes are set forth in the following table:

Coupling Component Amine (diazo component) Color (1) 2-methoxy-5-trifiuoroacetylamino-N-ethylaniline (2) 2-ethoxy-S-trifluoroncetylarhino-N-(fi-hydroxyethyl)-aniline. (3) 2- (fi-methoxyethoxy) -5-trifiuoroacetylamino -N (6 -hydroxyethoxy)-aniline. (4) 2- (,S-hydroxyethoxy) -5-trifiuoroacetylamino -N- (fl-hydroxyan e. (12) 2-methoxy-5-trifiuoroacetylamino-N-ethyl-N (fl,- -dihydroxypropyD-aniline. (13) 2-methoxy-5-irifluoroacetylamino-N-(B-hydroxyethyl)-N-(fi,'y-

dihydroxypropyl)aniline. (14) 2- trifiuoromethylthio -5 trifluoroacetylamino -N (15, dihydroxypropyD-eniline. 4

aniline. (16) 2-trifluoromothylthio-5-trifluoroacetylamino N,N -di-(fi-hydroxyethyD-aniline. I

p-nitroaniline .do .do

daemon floupling Component Amine (diazo. component) Dol.,. l.

p nitroo-fluoroanillne p-nitro-o-cblorouniline p nitroyo-bromoaniline 1 p-nitro -o-cyenoariiline ,1

- .violeLto red-blue.

blue to green-blue.

o-Fluoro-p nitroanillne which I employ as "a diazo component in-practicing my-invention 'can be prepared as follows:"32 g. (0.2+molel-of 4-, nitro-1,2-difluorobenzene and 140 cc; of28 per cent ammonia are heated together for *6 hours at -l50-to 160 C. in asteel liner of a-shaking autoclave. The mixture'is cooled *with shaking to room temperatur and the-mixture "of" water, ammonia,-and solid is poured-out; thediner is washed with water. -The crudegproduct is'filtered' from the liquors and recrystallized from methyl alcohol. The methyl alcohol solutionis filtered and then stirred and cooled inan icesalt bath while water is slowly added to the alcoholic solution until precipitation is complete. When filtered and-dried the 4-nitro- -fiuoroanii-ine weighs 26.4 g.,-which is '90 per cent of the theoretical amount of 43.8 g. The-melting point is 135 to-136 C.

The 1,2- difiuoro 4' --nitrobenzene employed abovecan -beprepared as follows: 25000201 concentratedsulfuric acid (sp. gr. 1.84) a and 220 g. "of concentrated nitric acid-*(sp. gr. 1:42) are mixed and cooled ta- C. While holding the temperature between 0 and 5 C., 162 g. of o-difluorobenzene are stirred in dropwise during-45 minutes. The temperature :drops after the addition is complete and the mixture is stirred eit lfl c. for one hour. Stirring is continued ior three hours while the temperature rises to 14 C. The temperature of the reaction is now raised to C. during minutes and stirring is continued at this temperature for 30 minutes. 625 g. of .cold water are now added. Thetemperature rises to to 50 C. The oil is dissolvedin carbon-tetrachloride and separated from the wateryliquors which are extracted again with carbon tetrachloride. The combined carbon tetrachloride liquors are washed with water; dilute'sodium-bicarbonate solution, and water. After the. final washing, the

carbon tetrachloride liquors are dried with calcium chloride overnight. The solvent is removed at atmospheric pressure at a'temperature up to D 2,4-dinitro-fiebromoaniline =D.o.

' 2,4-dinitr0-6-'icdoaniline 'Do. 2,4-dinitros6hyidroxyadil Do.

2,4-dinitro fi-triiluorometbylanilme D0.

2-amino-3g'5-dinitrophenylmethyi'ketoue. Do. 2aminof3,5-dinitrophenylmetbyl suiione. 0. Do. 2-amino-3;5=dinitrobenzene-N=methylsulfonamide Do. 2-amino 3,5.idinitrobenzene:N -,(fishydmxyethyl) 9.0.0.

sulionamide. Z-amino -3;'5-'dinitrobenzene N- (B-methoxyetbyl) Do. Msultonamide.

i a 25 Y N=N N l I a .2 HNffiTCE;

30 wherein Qwrepresents a member selected from the group consisting of a hydrogen atom ,and a nitrogroup, ylrepresents a member. selected .from thegrollp consisting or a hydrogen atom and a nitro group, at. least .one .of .the memberssQ .and Y being .a nitro ..g1: oup,, Z-represents a-member selected from. thegroup-consisting of. a hydrogen atom, a,.,halogen.atom, .a cyano group a .hydroxyl roup, a .ttifluoromethyl group, ahlow. carbon alkylketo .group, a...low carbon ,alkylsulfone emuna -S O 2N-'-low carbon alkyl group, a

carbon alkoxyalkyl group and a.

- carbon hydroxyalkyl group, X'represents a memher selected from 'the group consisting of a low carbon "alkoxy group, a low carbon thioalkyl i group and-a"trifiuoromethylthio group,'Rz:represents .amemberselectedvfrom the group consist- :ing of a hydrogen atom, a low carbon alkyl ggroup'and a low carbon hydroxyalkylgroup, and

R3 represents :a member selected from .the group consisting of a low. carbon al-kyl :group and a low carbon hydroxyalkyl group.

'2. An azo compound having the generalrforwherein R2 representsa low-carbon hydroxyalkyl ;group,"Rs represents a low carbon hydroxyalkyl group; 'X-represents a low carbon .alkoxy .group and Z represents a halogen atom.

9 3. An azo compound having the general formula:

NO; l X

wherein R2 represents a low carbon hydroxyalkyl group, R4 represents a low carbon alkyl group and X represents a low carbon alkoxy group.

4. An azo compound having the general formula:

wherein R2 represents a low carbon hydroxyalkyl group, R4 represents a low carbon hydroxyalkyl group and X represents a low carbon alkoxy group.

5. The azo compound of the following formula:

N02 OCH:

N0 N=N N CHa-CH-C'Hg 6. The azo compound of the following formula:

No, com

I cm-om-orr NOg- N=N N I OHr-CHz-OH Cl BIN-C O-GFa 7. The azo compound which can be represented by the following formula:

III 03 OCH; NOz- N=N N CHzCH-CH2 SO2NH N-C OCF3 I OH OH H1 JOSEPH B. DICKEY.

REFERENCES CITED The following references are of record in the 5 file of this patent:

UNITED STATES PATENTS Number Name Date 2,118,661 Baumann May 24, 1938 2,155,755 Felix et al. Apr. 25, 1939 Certificate of Correction Patent No. 2,436,100. February 17,- 1948. JOSEPH B. DIGKEY It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Column 2, in the formula, line 7, for Z read Z; column 7, line 40, for 43.8 g read 80.8 g; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 20th day of April, A. D. 1948.

THOMAS E MURPHY,

Assistant Commissioner of Patents. 

